JP2020015862A - Polyolefin nucleator, polyolefin nucleator composition containing the same, polyolefin resin composition, and molding thereof - Google Patents

Abstract

To provide a polyolefin nucleator that can improve the crystallization of polyolefin resin, a polyolefin nucleator composition containing the same, a polyolefin resin composition, and a molding thereof.SOLUTION: The present invention provides a polyolefin nucleator represented by formula (1) (where M: a univalent to trivalent metal atom, M: a hydrogen atom or the like, a: 1-3, b: 0-3, c: 1-3, x: 1-3, y: 1, t, u: 0-2, A: a direct bond or the like, B: an optionally substituted phenyl group or cyclohexyl group).SELECTED DRAWING: None

Description

  The present invention relates to a polyolefin nucleating agent, a polyolefin nucleating agent composition containing the same, a polyolefin-based resin composition, and a molded product thereof, and more particularly, to a polyolefin nucleating agent capable of improving crystallization of a polyolefin-based resin. The present invention relates to an agent, a nucleating agent composition for polyolefin containing the same, a polyolefin-based resin composition, and a molded article thereof.

  Polyolefin resins such as polyethylene, polypropylene, and polybutene-1 are inexpensive and have excellent properties such as moldability, hygiene, heat resistance, chemical resistance, mechanical properties, and low specific gravity. Widely used for various molded products such as electrical and electronic materials, textile materials, packaging materials, agricultural materials, housing materials for home appliances, household goods, medical equipment, food containers, beverage containers, films, sheets and structural parts. Have been. However, in order to enable such a wide range of use, it is necessary to satisfy physical properties required for products.

  It is known that the addition of a nucleating agent promotes the crystallization of a polyolefin-based resin during molding, and improves the transparency and physical properties of a molded product obtained by processing the polyolefin-based resin composition. Have been.

  As a nucleating agent for accelerating the crystallization of the polyolefin-based resin, a metal carboxylate, an organic phosphate, a benzylidene sorbitol compound, a metal rosinate, talc, and the like have been conventionally used. Among them, metal carboxylate such as sodium benzoate, aluminum salt of 4-tert-butyl benzoate, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, sodium bis (4 -Tert-butylphenyl) phosphate, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, lithium-2,2'-methylenebis (4,6-di-tert-butylphenyl) Polyvalent compounds such as phosphate ester compounds such as phosphate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol A Cole derivatives, N, N ', N "-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', N" -tricyclohexyl-1,3,5-benzenetricarboxamide, Amide compounds such as N, N'-dicyclohexylnaphthalenedicarboxamide and 1,3,5-tri (2,2-dimethylpropanamide) benzene are used as products exhibiting excellent nucleating agent effects in a small amount. Have been.

  With the diversification of uses of polyolefin-based resins, further improvement in performance is required, and it is required to expand the options of polyolefin nucleating agents. For example, Patent Document 1 proposes that an ionic compound composed of a carboxylate centered on a metal such as magnesium, calcium, and zinc be blended into polyethylene. Non-Patent Document 1 discloses that a metal salt of phenylmalonic acid exhibits an effect as a nucleating agent for polylactic acid.

JP 2014-525482 A Journal Macromolecular Science Part B: Physics (2016), 55 (2), p.128-137

  However, as proposed in Patent Document 1, when an ionic compound is blended with polypropylene, the nucleating agent effect is poor, such as the specific metal species restricting the nucleating agent effect, and further improvement is required. . In addition, since the nucleating agent effect is affected by the interaction generated between the crystal structure of the target resin and the crystal structure of the nucleating agent, the nucleating agent effect is exhibited by polylactic acid disclosed in Non-Patent Document 1. At present, sufficient investigation has not been made on compounds.

  Therefore, an object of the present invention is to solve these problems and improve the crystallization of polyolefin-based resin, a nucleating agent for polyolefin, a nucleating agent composition for polyolefin containing the same, a polyolefin-based resin composition, and It is in the molded product.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, a compound having a structure having a metal salt of a carboxylic acid and a cyclic group shows an excellent nucleating agent effect on polyolefin-based resins, particularly, on polypropylene-based resins. This led to the completion of the present invention.

（一般式（１）中、Ｍ^１は１〜３価の金属原子を表し、Ｍ^２は水素原子または１価の金属原子を表し、Ｍ^１の金属原子はヒドロキシ基と結合していてもよく、ａは１〜３を表し、ｂは０〜３を表し、ｃは１〜３を表し、ｘは１〜３を表し、ｙは１を表し、ｔ、ｕは各々独立して０〜２を表し、Ａは、直接結合、メチレン基、アミド結合、ウレア結合、ウレタン結合からなる群から選択される基若しくは結合を表し、Ｂは、下記一般式（２）、

（一般式（２）中、＊は、一般式（１）のＡと連結する位置を表し、Ｒ^０は、水素原子、ヒドロキシ基、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のハロゲンアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基からなる群から選択される基を表し、ｄは、０〜５の数を表し、複数のＲ^０を持つ場合は、複数のＲ^０が同一でもよく、一部または全部のＲ^０が異なっていてもよい。）
または、一般式（３）、

（一般式（３）中、＊は、式（１）のＡと連結する位置を表し、Ｒ^１は、水素原子、ヒドロキシ基、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のハロゲンアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基からなる群から選択される基を表し、ｅは、０〜５の数を表し、複数のＲ^１を持つ場合は、複数のＲ^１が同一でもよく、一部または全部のＲ^１が異なっていてもよい。）ただし、ａｘ＋ｂｙ＝２ｃの関係を満たす。）で表されることを特徴とするものである。 That is, the polyolefin nucleating agent of the present invention has the general formula (1):

(In the general formula (1), M ¹ represents a metal atom of ¹ to 3 valences, M ² represents a hydrogen atom or a monovalent metal atom, and the metal atom of M ¹ may be bonded to a hydroxy group. , A represents 1-3, b represents 0-3, c represents 1-3, x represents 1-3, y represents 1, t and u each independently represent 0-2. A represents a group or a bond selected from the group consisting of a direct bond, a methylene group, an amide bond, a urea bond, and a urethane bond, and B represents the following general formula (2):

(In the general formula (2), * represents a position linked to A in the general formula (1), and R ⁰ represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon atom Represents a group selected from the group consisting of a halogen alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and d represents a number of 0 to 5, If having a plurality of R ^0, it may be a plurality of R ⁰ are the same, or may be part or all of R ⁰ are different.)
Or, the general formula (3),

(In the general formula (3), * represents a position linked to A in the formula (1), and R ¹ represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon atom number. Represents a group selected from the group consisting of a halogenalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, e represents a number of 0 to 5, In the case of having R ¹ , a plurality of R ¹ may be the same, or some or all of R ¹ may be different.) However, the relationship of ax + by = 2c is satisfied. ).

In the polyolefin nucleating agent of the present invention, A in the general formula (1) is preferably a direct bond or an amide bond. In the polyolefin nucleating agent of the present invention, it is preferable that M ¹ and M ² in the general formula (1) are sodium, or that b = 0 and M ¹ is calcium or zinc.

  The polyolefin nucleating agent composition of the present invention comprises the polyolefin nucleating agent of the present invention, a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, other antioxidants, a hindered amine compound, and an ultraviolet absorber. And other nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, fatty acid metal salts, antistatic agents, pigments and dyes different from the compounds represented by the general formula (1). And at least one member selected from the group.

（一般式（４）中、Ｒ^２は、直鎖または分岐状の炭素原子数１２〜２０の脂肪酸残基を表し、該脂肪酸残基はヒドロキシ基で置換されていてもよく、Ｍ^３は、１〜３価の金属原子を表し、金属原子はヒドロキシ基と結合していてもよく、ｍは、１〜３の整数を表す。）であることが好ましい。ここで、脂肪酸残基とは、脂肪酸からカルボキシル基（−ＣＯＯＨ）を除いたものを意味する。 In the polyolefin nucleating agent composition of the present invention, the fatty acid metal salt is represented by the following general formula (4):

(In the general formula (4), R ² represents a linear or branched fatty acid residue having 12 to 20 carbon atoms, the fatty acid residue may be substituted with a hydroxy group, and M ³ is Represents a metal atom having 1 to 3 valences, and the metal atom may be bonded to a hydroxy group, and m represents an integer of 1 to 3.) Here, the fatty acid residue means a fatty acid obtained by removing a carboxyl group (—COOH) from a fatty acid.

  The polyolefin-based resin composition of the present invention contains 0.001 to 10 parts by mass of the polyolefin nucleating agent of the present invention with respect to 100 parts by mass of the polyolefin-based resin, or the polyolefin nucleating agent of the present invention contains 0.001 to 10 parts by mass. The nucleating agent composition for polyolefin of the present invention is contained in an amount of 10 parts by mass.

  In the polyolefin-based resin composition of the present invention, the polyolefin-based resin is preferably polypropylene.

  The molded article of the present invention is characterized by comprising the polyolefin resin composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the nucleating agent for polyolefin which can improve the crystallization of polyolefin-type resin, the nucleating agent composition for polyolefin containing this, the polyolefin-type resin composition, and its molded article can be provided. . The nucleating agent for polyolefin of the present invention can greatly raise the crystallization temperature of the polyolefin-based resin, and particularly when the resin is a polypropylene-based resin, the improvement effect is extremely high.

で表される化合物である。ここで、一般式（１）中、Ｍ^１は１〜３価の金属原子を表し、Ｍ^２は水素原子または１価の金属原子を表し、Ｍ^１の金属原子はヒドロキシ基と結合していてもよく、ａは１〜３を表し、ｂは０〜３を表し、ｃは１〜３を表し、ｘは１〜３を表し、ｙは１を表し、ｔ、ｕは各々独立して０〜２を表し、Ａは、直接結合、メチレン基、アミド結合、ウレア結合、ウレタン結合からなる群から選択される基若しくは結合を表す。ただし、ａｘ＋ｂｙ＝２ｃの関係を満たす。 Hereinafter, embodiments of the present invention will be described in detail.
The nucleating agent for polyolefin of the present invention has the following general formula (1):

It is a compound represented by these. Here, in the general formula (1), M ¹ represents a divalent metal atom, M ² represents a hydrogen atom or a monovalent metal atom, and the metal atom of M ¹ is bonded to a hydroxy group. A represents 1 to 3, b represents 0 to 3, c represents 1 to 3, x represents 1 to 3, y represents 1, t and u each independently represent 0. And A represents a group or a bond selected from the group consisting of a direct bond, a methylene group, an amide bond, a urea bond, and a urethane bond. However, the relationship of ax + by = 2c is satisfied.

B in the general formula (1) represents the following general formula (2) or general formula (3).

Here, in the general formula (2), * represents a position linked to A in the general formula (1), and R ⁰ is a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, Represents a group selected from a halogen alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms; d represents 0 to 5; ^When it has ⁰ , a plurality of R ⁰ may be the same, or some or all of R ⁰ may be different.

In the general formula (3), * represents a position linked to A in the general formula (1), and R ¹ is a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon atom number. Represents a group selected from a halogen alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, e represents 0 to 5, and has a plurality of R ¹ In this case, a plurality of R ¹ may be the same, or some or all of R ¹ may be different.

The trivalent metal atom constituting M ¹ in the general formula (1) includes lithium, sodium, potassium, silver, calcium, barium, copper, zinc, magnesium, manganese, aluminum and the like. May have a hydroxy group. Preferred metal atoms for the polyolefin nucleating agent of the present invention include lithium, potassium, sodium, zinc, calcium, hydroxyaluminum and the like.

The monovalent metal atom represented by M ² in the general formula (1) includes lithium, sodium, potassium, silver, and the like. Preferred metal atoms of the polyolefin nucleating agent of the present invention include alkali metal atoms, and more preferably sodium.

Examples of the halogen atom represented by R ⁰ in the general formula (2) and R ¹ in the general formula (3) include fluorine, chlorine, bromine and iodine. In the nucleating agent for polyolefin of the present invention, Chlorine is particularly preferred.

As the alkyl group having 1 to 10 carbon atoms represented by R ⁰ in the general formula (2) and R ¹ in the general formula (3), a linear or branched alkyl group, or 3 to 10 carbon atoms A cycloalkyl group. Specifically, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, cyclobutyl, amyl, tert-amyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, isooctyl Tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl and the like.

As the alkoxy group having 1 to 10 carbon atoms represented by R ⁰ in the general formula (2) and R ¹ in the general formula (3), a linear or branched alkoxy group, or an alkoxy group having 5 carbon atoms And 10 to 10 cycloalkoxy groups. Specifically, for example, methoxy, ethoxy, n-propoxy, n-butoxy, n-hexyloxy, 1-methylethoxy, 2-methylpropoxy, 1-methylbutoxy, 4-methylpentyloxy, cyclohexyloxy and the like can be mentioned. Can be

Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ⁰ in the general formula (2) and R ¹ in the general formula (3) include vinyl, anil, propenyl, butenyl, hexenyl, oleyl, and decenyl. Can be mentioned. The position of the double bond may be at the α-position, at the inside, or at the ω-position.

The nucleating agent for polyolefin of the present invention is more preferably a compound represented by the following general formulas (5) to (10).

  Specific examples of the nucleating agent for polyolefin of the present invention include the following compounds. However, the nucleating agent for polyolefin of the present invention is not limited to these.

  The polyolefin nucleating agent of the present invention is an additive to be blended in the polyolefin resin, and can be used in combination with other additives blended in the polyolefin resin. In this case, the polyolefin nucleating agent of the present invention and other additives may be separately added to the polyolefin-based resin, or the polyolefin nucleating agent of the present invention and other additives may be mixed to form a polyolefin nucleating agent. May be used as an agent composition. The compounding amount of the polyolefin nucleating agent of the present invention can be used without any particular limitation, but the polyolefin nucleating agent of the present invention is in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin-based resin. It is preferable to mix them so as to be more preferably 0.005 parts by mass to 1 part by mass. However, when used as a master batch containing a high concentration of a nucleating agent, the compounding amount of the nucleating agent for polyolefin of the present invention may exceed the upper limit of 10 parts by mass.

  Other additives that can be used in combination with the polyolefin nucleating agent of the present invention do not significantly impair the nucleating agent effect of the polyolefin nucleating agent of the present invention, or increase the performance of the obtained polyolefin-based resin composition. It is not limited unless it is damaged. As such other additives, additives generally used in polyolefin resins, for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, other antioxidants, hindered amine compounds , Ultraviolet absorbers, other nucleating agents different from the compound represented by the general formula (1), flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, fatty acid metal salts, antistatic agents, pigments And dyes. The compounding amount of the other additives used in combination with the nucleating agent for polyolefin of the present invention can be used without any particular limitation. However, the compound represented by the general formula (1) and the other additives are suitably used in the polyolefin resin. It is preferable that the compound is formulated so as to be present at an appropriate concentration.

  Phenolic antioxidants include, for example, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), 2,2′-thiodiethylenebis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- ( , 5-Di-tert-butyl-4-hydroxyphenyl) propionamide, 2,2'-oxamido-bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2 -Ethylhexyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-tert-butylphenol), 3,5-di -Tert-butyl-4-hydroxybenzenepropanoic acid and an ester of C13-15 alkyl, 2,5-di-tert-amylhydroquinone, a polymer of hindered phenol (trade name “AO.OH.98, manufactured by Adeka Palmarol Co., Ltd.) "), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2-tert Butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl]- 4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butylbenz [d , F] [1,3,2] -dioxaphosphobin, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3,5-di -Tert-butyl-4-hydroxybenzyl) phosphonate] calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 (3H ) -Reaction product of benzofuranone with o-xylene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, DL -A-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3-bis- (4′-hydroxy-3′-tert-butyl-phenyl) Butanoic acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-tert-butyl 4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2- Octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3 3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4′-butylidenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (6-tert -Butyl-3-methylphenol), 2,2′-ethylidenebis (4,6-di-tert-butyl) Phenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert) -Butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, , 3,5-Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [me Len-3- (3 ', 5'-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5 -Methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10- Tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionamide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) p Lopionamide, myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid Examples include 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as amides. When the phenolic antioxidant is compounded, the amount is preferably 0.001 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, based on 100 parts by mass of the polyolefin resin. Is preferred.

  Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, and diphenyl triphosphite. Decyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, dioleyl hydrogen phosphite, trilauryl trithio phosphite, bis (tridecyl) phosphite, tris ( (Isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenylbis (nonylphenyl) phosphite, poly (dipropylene glycol) Coal) phenyl phosphite, tetraphenyl dipropyl glycol diphosphite, tris nonyl phenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5) -Methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tri (decyl) phosphite, Octyl diphenyl phosphite, di (decyl) monophenyl phosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite , Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2 -Tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4- Di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene) tris (1 , 1-dimethylethyl) -5-methyl-4,1-phenylene) hexatrideci Phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4'-butylidenebis (3-methyl-6-tert-butylphenylditridecyl) phosphite, tris (2- [(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl) oxy] ethyl) amine, 3,9-bis ( 4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphesspiro [5,5] undecane, 2,4,6-tri tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4′-isopropylidene diphenol C12-15 alcohol phosphite, bis (diisodecyl) pentaerythritol diphosphite, bis (Tridecyl) pentaerythritol diphosphite, bis (octadecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-diphenyl) Mill phenyl) pentaerythritol diphosphite, and the like. When the phosphorus-based antioxidant is blended, the blending amount is adjusted to be 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the polyolefin resin. Is preferred.

  Thioether-based antioxidants include, for example, tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl) Sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate , Lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), distearyl-disulfide Is mentioned. When the thioether-based antioxidant is blended, the blending amount is adjusted to be 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the polyolefin-based resin. Is preferred.

  Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) ) Benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 -Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert- Octyl-6-benzotriazolylphenol), 2- (2-hydroxy Polyethylene glycol ester of 3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy- 3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, -[2-hydroxy-3- tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2- Hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [ 2- (2-hydroxy) such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole and 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Phenyl) benzotriazoles; Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate , Dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4) Benzoates such as -hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate and behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2 '-Ethoxyoxanilide, 2-ethoxy-4'-dodecy Substituted oxanilides such as oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, trioctyl-2,2 ′, 2 ″-((1,3,5-triazine-2,4,6-triyl) tris (3-hydroxybenzene-4-, 1- Diyl) tripropionate), 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] pheno , 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine, 1,12-bis [2- [4- (4,6-diphenyl- Triazines such as 1,3,5-triazin-2-yl) -3-hydroxyphenoxy] ethyl] dodecandioate; various metal salts or metal chelates, particularly nickel or chromium salts or chelates. Can be The blending amount when blending the ultraviolet absorber is adjusted to be 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the polyolefin resin. Is preferred.

  The hindered amine compound is, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetra Methyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,3 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetra Methyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di- tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis ( 2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetra Methyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N − (2,2, , 6-Tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, bis} 4- (1-octyloxy-2,2,6,6-tetra Methyl) piperidyl} decandionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl} carbonate and the like. When the hindered amine compound is compounded, the compounding amount may be adjusted to 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the polyolefin resin. preferable.

  Other nucleating agents include, for example, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and lithium-2,2'-methylenebis (4,6-di-tert-butylphenyl). ) Phosphate, aluminum hydroxybis [2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate], sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate and disodium bicyclo [ 2.2.1] Metal salts of carboxylic acids such as heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) ) Sorbitol, and bis ( Polyol derivatives such as methylbenzylidene) sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-((4-propylphenyl) methylene) nonitol, N, N ′, N ″ -tris [ 2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N ', N "-tricyclohexyl-1,3,5-benzenetricarboxamide, N, N'-dicyclohexylnaphthalenedicarboxamide, 1,3 Amide compounds such as 1,5-tri (dimethylisopropoylamino) benzene. When the other nucleating agent is compounded, the compounding amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the polyolefin resin.

  Flame retardants include, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methylethylidene)- 4,1-phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade names “ADEKA STAB FP-500”, “ADEKA STAB FP-600”, “ADEKA STAB FP-” manufactured by ADEKA Corporation 800 "aromatic phosphates, phosphonates such as divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, diphenylphosphite Phosphinates such as methyl acid, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresylphosphazene, melamine phosphate, Melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-based flame retardants such as phosphorus-containing vinylbenzyl compounds and red phosphorus, magnesium hydroxide, aluminum hydroxide Such as metal hydroxides, brominated bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromo Phthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4 , 6-Tris (tribromophenoxy) -1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate, and bromination Brominated flame retardants such as styrene can be mentioned. These flame retardants are preferably used in combination with an anti-drip agent such as a fluororesin or a flame retardant aid such as a polyhydric alcohol or hydrotalcite. It is preferable to adjust the amount of the flame retardant to be 1 to 100 parts by mass, more preferably 10 to 70 parts by mass, based on 100 parts by mass of the polyolefin resin.

  The lubricant is added for the purpose of imparting lubricity to the surface of the molded article and enhancing the effect of preventing damage. As the lubricant, for example, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmititate, Sorbitan monostearate, mannitol, stearic acid, hardened castor oil, stearin sun amide, oleic amide, ethylene bisstearic amide and the like can be mentioned. These may be used alone or in combination of two or more. The blending amount in the case of blending the lubricant is preferably adjusted to 0.01 to 2 parts by mass, more preferably to 0.03 to 0.5 parts by mass, based on 100 parts by mass of the polyolefin resin. .

  Hydrotalcites are complex salt compounds composed of magnesium, aluminum, a hydroxyl group, a carbonate group and any water of crystallization known as natural products and synthetic products, and a part of magnesium or aluminum is converted to another metal such as alkali metal or zinc. And those obtained by substituting a hydroxyl group or a carbonate group with another anion group. Specifically, for example, a metal of hydrotalcite represented by the following general formula (11) is substituted with an alkali metal. Things. Further, as the Al-Li-based hydrotalcites, a compound represented by the following general formula (12) can also be used.

ここで、一般式（１１）中、ｘ１およびｘ２はそれぞれ下記式、
０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０
で表される条件を満たす数を表し、ｐは０または正の数を表す。

Here, in the general formula (11), x1 and x2 are the following formulas, respectively.
0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20
And p represents 0 or a positive number.

ここで、一般式（１２）中、Ａ^ｑ−は、ｑ価のアニオンを表し、ｐは０または正の数を表す。また、ハイドロタルサイト類における炭酸アニオンは、一部を他のアニオンで置換したものでもよい。

Here, in the general formula (12), A ^q- represents a q-valent anion, and p represents 0 or a positive number. Further, the carbonate anion in the hydrotalcites may be one in which a part is substituted with another anion.

  Hydrotalcites may be obtained by dehydrating water of crystallization, and may be higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, or organic metal sulfonates such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, a higher fatty acid amide, a higher fatty acid ester or a wax.

  The hydrotalcites may be natural products or synthetic products. Examples of the method for synthesizing hydrotalcites include JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, and JP-A-61-174270. And a known method described in JP-A-5-179052. In addition, hydrotalcites can be used without being limited by their crystal structure, crystal particles, and the like. The blending amount in the case of blending hydrotalcites is adjusted to be 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the polyolefin resin. preferable.

  Examples of fatty acid metal salts include, for example, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, isostearic acid Saturated fatty acids such as stearic acid, 12-hydroxystearic acid, arachidic acid, henycosylic acid, behenic acid, lignoceric acid, montanic acid, crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, Vaccenic acid, gadolinic acid, eicosenoic acid, erucic acid, nervonic acid and other unsaturated fatty acids, linoleic acid, eicosadienoic acid, diunsaturated fatty acids such as docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, Eicosatrienoic acid, stearidonic acid, Rakidon acid, eicosatetraenoic acid, Adoen acid, unsaturated bond such as docosahexaenoic acid is 3 or more unsaturated fatty acids. When used in combination with the nucleating agent for polyolefin of the present invention, fatty acids having 12 to 20 carbon atoms such as lauric acid, myristic acid, stearic acid, and 12-hydroxystearic acid are more preferred.

  Examples of the metal used for the fatty acid metal salt include sodium, potassium, lithium, calcium, zinc, barium, magnesium, and aluminum, and may have a hydroxy group.

で表される化合物が好ましい。ここで、一般式（４）中、Ｒ^２は、直鎖または分岐状の炭素原子数１２〜２０の脂肪酸残基を表し、脂肪酸残基はヒドロキシ基で置換されていてもよい。Ｍ^３は、１〜３価の金属原子を表し、金属原子はヒドロキシ基と結合していてもよく、ｍは、１〜３の整数を表す。 Among these fatty acid metal salts, from the viewpoint of obtaining heat resistance and the effect of dispersing the nucleating agent in the resin, the following general formula (4):

The compound represented by is preferred. Here, in the general formula (4), R ² represents a linear or branched fatty acid residue having 12 to 20 carbon atoms, and the fatty acid residue may be substituted with a hydroxy group. M ³ represents a metal atom having 1 to 3 valences, the metal atom may be bonded to a hydroxy group, and m represents an integer of 1 to 3.

In the general formula (4), specific examples of M ³ include sodium, potassium, lithium, calcium, zinc, barium, magnesium, hydroxy aluminum and the like, sodium, potassium, lithium is particularly preferred.

  Examples of the antistatic agent include cationic antistatic agents such as quaternary ammonium ion salts of fatty acids and polyamine quaternary salts; higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, and anionic alkyl sulfones. Anionic antistatic agents such as acid salts, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates, etc .; polyhydric alcohol fatty acid esters, polyglycol phosphates, polyoxyethylene Nonionic antistatic agents such as alkyl allyl ethers; amphoteric antistatic agents such as amphoteric alkyl betaines such as alkyldimethylaminoacetate betaine and the like, imidazoline amphoteric surfactants, and polymeric antistatic agents such as polyetheresteramide And the like. Such an antistatic agent may be used alone, or two or more antistatic agents may be used in combination. The amount of the antistatic agent to be added is adjusted to be 0.03 to 2 parts by mass, more preferably 0.1 to 0.8 parts by mass, based on 100 parts by mass of the polyolefin resin. Is preferred.

  As the pigment, a commercially available pigment can also be used, for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 09, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 29, 56, 60, 61, 62, 64; Pigment Violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

  The fluorescent whitening agent is a compound which absorbs ultraviolet rays of sunlight or artificial light, converts the ultraviolet rays into visible light of violet to blue, and radiates the same, thereby promoting the whiteness and blue tint of the molded article. Benzoxazole compounds C.I. I. Fluorescent Brightner 184; Coumarin-based compound C.I. I. Fluorescent Brightner 52; diaminostilbene disulfonic acid compound C.I. I. Fluorescent Brightner 24, 85, 71 and the like. The compounding amount when using the fluorescent whitening agent is adjusted to be 0.00001 to 0.1 part by mass, more preferably 0.00005 to 0.05 part by mass, based on 100 parts by mass of the polyolefin resin. Is preferred.

  As the dye, azo dye, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, phthalocyanine dye And a dye such as a cyanine dye. These may be used as a mixture of two or more.

Next, the polyolefin resin composition of the present invention will be described.
The polyolefin resin composition of the present invention contains 0.001 to 10 parts by mass of the polyolefin nucleating agent of the present invention with respect to 100 parts by mass of the polyolefin resin. The polyolefin resin used in the polyolefin resin composition of the present invention is not particularly limited. For example, low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), high density polyethylene (HDPE), isotactic polypropylene, syndiotactic polypropylene, hemi-isotactic polypropylene, cycloolefin polymer, stereo block Α-olefin polymers such as polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or random copolymer, impact Copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, Len - vinyl alcohol resin (EVOH) can α- olefin copolymers, and the use of such, or may be elastomer comprising a polyolefin resin. In the present invention, two or more of these may be used as a blend, a block copolymer may be formed and used as a block polymer type, or the resin may be alloyed. Further, chlorinated products of these olefin resins may be used.

  As the elastomer of the polyolefin resin, using a polyolefin such as polypropylene or polyethylene as a hard segment, a rubber such as an ethylene-propylene rubber as a soft segment, an elastomer obtained by blending them, or an elastomer obtained by dynamic crosslinking Is mentioned. Examples of the hard segment include at least one selected from a polypropylene homopolymer, a polypropylene block copolymer, a polypropylene random copolymer, and the like. Examples of the soft segment include an ethylene-propylene copolymer (EPM), an ethylene-propylene-diene copolymer (EPDM), an ethylene-vinyl acetate copolymer (EVA), and a vinyl acetate homopolymer. You may blend and use these 2 or more types.

  The method for producing the olefin-based resin includes a Ziegler catalyst, a Ziegler-Natta catalyst, a metallocene catalyst and various other polymerization catalysts as cocatalysts, a catalyst carrier, a chain transfer agent, and also a gas phase polymerization, a solution polymerization, an emulsion polymerization, In various polymerization methods such as bulk polymerization, various polymerization conditions such as temperature, pressure, concentration, flow rate, removal of catalyst residues, etc. can be used to obtain resins suitable for packaging materials and physical properties suitable for molding processing of packaging materials The resin is obtained by appropriately selecting a resin from which the resin is obtained. Number average molecular weight, weight average molecular weight, molecular weight distribution, melt flow rate, melting point, melting peak temperature, stereotacticity such as isotactic and syndiotactic, presence or absence and degree of branching, specific gravity of olefin resin, and various solvents The ratio of dissolved components, haze, gloss, impact strength, flexural modulus, Olsen stiffness, other properties, and whether or not each property value satisfies a specific equation can be appropriately selected according to desired properties. .

  The method of blending the polyolefin nucleating agent of the present invention with the polyolefin-based resin is not particularly limited, and a generally used method, for example, a method of dry-blending the polyolefin-based resin powder or pellets with the nucleating agent, and a method of using a high nucleating agent. There is a method of preparing a master batch containing the same in a concentration and adding the same to a polyolefin-based resin, and a method of processing a nucleating agent and other additives into pellets and adding them to the polyolefin-based resin. Further, the nucleating agent and other additives may be added to the olefin resin at the same time, or may be added separately.

  As a method for processing into a pellet shape, a mixture of a nucleating agent, a phenolic antioxidant, a polymer compound, a binder such as a petroleum resin, and an optional additive optionally contained therein are heated to form a binder in a molten state. It can be produced by mixing in the presence. Processing conditions, processing equipment, and the like are not particularly limited, and well-known general processing methods and processing equipment can be used. Specific production methods include a disk pelletizer method, an extrusion method, and the like.

  In the polyolefin resin composition of the present invention, the amount of the polyolefin nucleating agent of the present invention is 0.001 to 10 parts by mass, preferably 0.005 to 1 part by mass, based on 100 parts by mass of the polyolefin resin. It is. If the amount is less than 0.001 part by mass, the nucleating agent effect may not be obtained. If the amount exceeds 10 parts by mass, dispersion in the polyolefin resin becomes difficult, and the physical properties and appearance of the molded product are adversely affected. May be.

  In the polyolefin-based resin composition of the present invention, any known additives (for example, phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, and other antioxidants can be used as long as the effects of the invention are not significantly impaired. Agent, hindered amine compound, ultraviolet absorber, other nucleating agent different from the compound represented by formula (1), flame retardant, flame retardant auxiliary, lubricant, filler, hydrotalcite, fatty acid metal salt, charging Inhibitors, fluorescent brighteners, pigments, dyes, etc.). These additives are the same as those described above.

  The molded article of the present invention comprises the polyolefin-based resin composition of the present invention. The polyolefin-based resin composition of the present invention can be molded using a known molding method. For example, it is possible to obtain a molded product by using an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calendar molding method, a slash molding method, a dip molding method, a foam molding method, or the like. .

  Examples of the use of the polyolefin resin composition of the present invention include automobile materials such as bumpers, dashboards, instrument panels, housing uses such as refrigerators, washing machines, and vacuum cleaners, tableware, buckets, household goods such as bath articles, and miscellaneous goods such as toys. Articles, storage articles such as tanks, molded articles such as storage containers, films, fibers and the like.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited by the following Examples and the like.

[Examples 1-1 to 1-9, Comparative Example 1-1]
As the polyolefin resin, 100 parts by mass of homopolypropylene (melt flow rate: 8 g / 10 min; 2.16 kg × 230 ° C. based on ISO standard 1133) is added to a phenolic antioxidant (tetrakis [methylene-3- (3 ′, 5 ′)). -Tert-butyl-4'-hydroxyphenyl) propionate] methane) 0.05 parts by mass, phosphorus-based antioxidant (tris (2,4-di-tert-butylphenyl) phosphite) 0.1 parts by mass, stir After mixing 0.05 parts by mass of a calcium phosphate salt and the compounds shown in Table 1 with a Henschel mixer under a condition of 1,000 rpm × 1 minute, these are blended, and then a twin screw extruder (TEX-28V; (Manufactured by Nippon Steel Corporation) at an extrusion temperature of 230 ° C. In addition, Comparative Example 1-1 was granulated by the same procedure as Example 1-1 except that the compound was not blended. After the granulated pellets were dried at 80 ° C. for 8 hours, they were evaluated under the following conditions.

<Crystallization temperature Tc [° C]>
Using the obtained pellet, the crystallization temperature (Tc) was measured using a differential scanning calorimeter (apparatus; diamond manufactured by Perchielmer). The measurement method is as follows: in a chart obtained by heating from room temperature to 230 ° C. at a rate of 50 ° C./min, holding for 10 minutes, and cooling to −50 ° C. at −10 ° C./min, the endothermic reaction has a peak top. The temperature was taken as the crystallization temperature (° C.).

<Flexural modulus [MPa]>
Using the obtained pellets, an injection molding machine (equipment: EC100-2A; manufactured by Toshiba Machine Co., Ltd.) was used to perform injection molding under the conditions of a mold temperature of 40 ° C. and a resin temperature of 230 ° C. to obtain a size of 80 mm × 10 mm × 4 mm. Test pieces were prepared. Immediately after the injection molding, the test piece was allowed to stand in a thermostat at 23 ° C. for 48 hours or more, and then, using a bending tester (AG-IS; manufactured by Shimadzu Corporation), in accordance with ISO 178, flexural modulus (MPa). ) Was measured.

[Examples 2-1 to 2-16, 3-1 to 3-4, Comparative Examples 2-1, 2-2, 3-1 and 3-2]
As a polyolefin resin, 100 parts by mass of a homopolypropylene (melt flow rate: 8 g / 10 min; 2.16 kg × 230 ° C. based on ISO standard 1133) is added to a phenolic antioxidant (tetrakis [methylene-3- (3 ′, 5 ′)). -Tert-butyl-4'-hydroxyphenyl) propionate] methane) 0.05 parts by mass, phosphorus-based antioxidant (tris (2,4-di-tert-butylphenyl) phosphite) 0.1 parts by mass, stir After mixing 0.05 parts by mass of calcium phosphate and the compounds described in Table 2 or 3 with a turbula mixer for 5 minutes, a twin screw extruder (Laboplast Mill μ; manufactured by Toyo Seiki Seisaku-sho, Ltd.) is used. At an extrusion temperature of 230 ° C. In addition, Comparative Example 2-1 and Comparative Example 3-1 were granulated by the same procedure as Example 2-1 except that the compound was not blended. After drying the granulated pellets at 80 ° C. for 8 hours, the crystallization temperature Tc [° C.] was evaluated in the same procedure as above.

  Table 2 shows that in the case of the compound having an amide bond, although there is a difference in the nucleating agent effect depending on the optical isomer, an excellent nucleating agent effect is obtained. Also, by comparing Example 3-3 in Table 3 with Examples 2-8 and 2-9 in Table 2, the compound in which Y in the general formula (1) has a substituent is excellent in the nucleating agent effect. Was confirmed.

Claims (10)

General formula (1),

(In the general formula (1), M ¹ represents a metal atom of ¹ to 3 valences, M ² represents a hydrogen atom or a monovalent metal atom, and the metal atom of M ¹ may be bonded to a hydroxy group. , A represents 1-3, b represents 0-3, c represents 1-3, x represents 1-3, y represents 1, t and u each independently represent 0-2. A represents a group or a bond selected from the group consisting of a direct bond, a methylene group, an amide bond, a urea bond, and a urethane bond, and B represents the following general formula (2):

(In the general formula (2), * represents a position linked to A in the general formula (1), and R ⁰ represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon atom Represents a group selected from the group consisting of a halogen alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and d represents a number of 0 to 5, If having a plurality of R ^0, it may be a plurality of R ⁰ are the same, or may be part or all of R ⁰ are different.)
Or, the general formula (3),

(In the general formula (3), * represents a position linked to A in the formula (1), and R ¹ represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon atom number. Represents a group selected from the group consisting of a halogen alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, e represents a number of 0 to 5, In the case of having R ¹ , a plurality of R ¹ may be the same, or some or all of R ¹ may be different.) However, the relationship of ax + by = 2c is satisfied. A nucleating agent for polyolefins, characterized by being represented by:   2. The polyolefin nucleating agent according to claim 1, wherein A in the general formula (1) is a direct bond or an amide bond. 3. The nucleating agent for polyolefin according to claim 1, wherein M ¹ and M ² in the general formula (1) are sodium. 3. The polyolefin nucleating agent according to claim ¹ , wherein b = 0 in the general formula (1) and M1 is calcium or zinc.   The polyolefin nucleating agent according to any one of claims 1 to 4, a phenolic antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, other antioxidants, a hindered amine compound, an ultraviolet absorber, A group consisting of other nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, fatty acid metal salts, antistatic agents, pigments and dyes different from the compounds represented by the general formula (1) A nucleating agent composition for polyolefins, comprising: at least one selected from the group consisting of: The fatty acid metal salt is represented by the following general formula (4):

(In the general formula (4), R ² represents a linear or branched fatty acid residue having 12 to 20 carbon atoms, the fatty acid residue may be substituted with a hydroxy group, and M ³ is The nucleating agent composition for a polyolefin according to claim 5, wherein the nucleating agent composition is a monovalent to trivalent metal atom, and the metal atom may be bonded to a hydroxy group, and m represents an integer of 1 to 3.   A polyolefin resin composition comprising 0.001 to 10 parts by mass of the polyolefin nucleating agent according to any one of claims 1 to 4 based on 100 parts by mass of the polyolefin resin.   The nucleating agent composition for polyolefin according to claim 5 or 6, such that the nucleating agent for polyolefin according to any one of claims 1 to 4 is 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. A polyolefin-based resin composition characterized by containing a substance.   9. The polyolefin resin composition according to claim 7, wherein the polyolefin resin is polypropylene. A molded article comprising the polyolefin resin composition according to any one of claims 7 to 9.